Preparation of naphthols



Y lbe usedzlheated to atemperature of 350iJ to`360 (llrin'aboui'.v mi .one-half hour, :and thereat maintained for Vone lenewas reacted` With1.25 mols of aqueous 105per l cent sodiumhydrfoxide forfone hourf at;350? yto sodium hydroxide in an iron'reac'tor'for one hourA ati350fto 360"vr C.; obtaining therebyeaV practically thols, respectively.

A approximately l 60 percent and .40 l per cent, fre-1 oi the 'various'l ways in which our invention may Example 1 l 'A mixtureof 1 mol of monochloronaphthalone'4 (consisting of 98.5 percent alphaand 1.5 per' cent beta-chloro isomers), and 2.5 mols of sodium hydroxide in 10.v per cent 'aqueous solution `Was hour in anv iron reactor, thereby obtaining a 961.5 per cent conversion. '.The aqueousireactionjmixj ture was removed from theV bomb, acidied withA hydrochloric acid,` and theCmde naphthols to- Vgether with Vethers separatedtherefjrom'by filtra` tion, and then vfractionallydistilled.. The so'obper cent and4`4 per cent of alphaiand b eta-naphf thols; respectively..` As a byproductthere was ob#y alpha and 22.5 vperlc'ei'it of beta'modifcations) was reacted with `V1 'kilogram' of 9.8 51-per `cent aqueous quantitative conversion.Y VTheV 'c :rude'V reaction product comprisedfO'? molof'naphthols (51 per-V` cent `andfl'per cent of falphaandubeta'modica-l tions,` respectively) jand V0.15'n 1o lfofV dinaphthyl 360i?` C.; therebyobtaining a.961per cent, conversion,-,and` a naphthol productvconsistingfof 78 f per cent` and 22,-per cent'fof betal and'alphafnaphantple 4"v Inlike mannenalpha-chloronaphthalene'(eqntainingpercent'offthe beta isomer) .was hydro;

iyzedwitnaqueops sodium carbonate at 3suisses C.; obtainingfthereby aa practically-l quantitative conversionlandt a naphtholg product containing sp'ectively, of alpha and beta-naphtholsn Similarlyfalphaechloronaphthalene (containe-v ing 8v pcri'cent oi? the Vbeta modiiication) Was f hydrolyzed.'Y with aqueous sodium .borate at i "3509-4360C. The 'chloronaphthalene was hydrolyzedlto about190 per cent to forma crude productv from which a naphthol-product wasobtained which contained approximately '49 .per cent and of naphthols bythe hydrolysis 4of bromo or Ychlorof naphthalenefor 'alkylv derivatives I th'ereofj (the correspondingiodo compounds beingexcluded) to .form a' crudereac'tion productf comprising a .ture of lan unexpected -naphthol -ivhrein hydrogen' occupies theoriginalhalog'en position andthe hydroxy group is'ortho thereto,'-1together witl'rthe zo' lhas`directly vreplacedthe halogen, such hydrolysis' being carried out'jat "temperatures f'betweer'liBOO'if- FQ and 400Y C. intlfiefpresenceiofjafhydrolytic agent fromV the groupf comprisingan alkalifmetal hy-l expected naphtholji; e; wherein' the hydroxy group y compound.

naphthols'and naphthyl others,

or'mr suoli agents, or .equivalent thereof, and in the substantialabsence of copper. In the Vco l pending application `of E. C;.Britton, Serial No.

519,692,` filed March 2, 1931` it has been shown-that therel isV no substantial formation of isomeric phenols in "hydrolytic reactions of the character ,infhandwhen a copper-containingcatalyst; par- 'ticularly metallic copper, is present. It isessential-,'then, that copper be absent for vaccomplisliing the substitution` of hydroxyl in a position in thearomaticnucleus other thanthat occupied by 4 Vthe'halogen originally; in order to carry out'the process in accordance lwith the present inven-J tionpl` 'l 'f v' 1 The novel products obtainable by theherein [described hydrolysis, e. gra mixture of alphaand betanapl'itholsfwith or without accompanying dinaphthyl ethers or mixed dinaphthyl ethers ,and in varying proportions (dependent on the, conditionsof the hydrolysis) may advantageously beemployed as. such ,wi thout further unnecessary separationinto individual vconfiponents'thereof for antiseptic, insecticidal, 'or other purposes.

In vthe claims, by the expression in the absence:

of copper?, we mean copper which is in a form capable of Aactingcatalytically in the liyfdrolyticy reaction, e. gra copper. inner-surface of the readtor, copper powder not in contact Witha less noble metal-'..suchas iron, ora dissolved copper come..- `vpound'such as cuprous oxide.

Otherl modes-of applying the principle of our invention may Vbe employedY instead of those exa-i plained, change being made as regards the. de f vtailsY herein disclosed, providedlthestep or steps starmiv by any of the following 'claims or the so equivalent thereof be employed. f I

g We. therefcnfek particularly point out and dis-"lf tinctlyclaim as-.our invention: -J` '.1'. The method :of making amixture monochloronaphthalene vvith approximatelyfl of catalytically active metallic copperor copper pfalpha and beta-napl'ithols which' comprises-reactingfafloiA Y f mols to. 5. mols lofaqueous sodium hydroxideof 13` I f to 2 5 per cent concentration, under pressure, at a temperatureof300 to 400 C., Aand, in the absence 2.'The' v'method i of' making 'alphai-naphthol" f3.' The methodof makingfbeta-naphthol vvhichf.

`Which comprises reacting a mixture of alpha andl 'beta-chloronaphth'alenes With approximately 1.5

mols to 5 mols'ofaqueous sodium hydroxideof 3 to 25 percentconcentration, under pressure`,1at va temperatureof ,300? to4f00" C., inthe absenceof ocatalyticallyy'activef metallic copper ,orjcopperf comprises Yreacting .a' mixture o f alpha and beta-lf chloronaphthalenes with approximately 1.51no1s f' 51"per1cent, respectivelygfof alpha and beta-naph- A y g 1 -25f`pe`rcent concentration,runder pressure, at'aL A, Inbrief;ourinvention'concerns the preparationV callylytically active metallic copper for, copper compound; and separating betanaphthol vfrom f thereactiomixture comprisingfalphaand beta- 1 4. The method of` making-j a1 hydroxide of,` 3 to;2 5per cent concentration, under :g

',ppressure, at atemperature of V300 to 4009. C.; in: :theabs'ence'of catalyti'callyactive'inetallic copper orcopperl compound, and l separating alpha vand 75 ae Cil beta-naphthols from the reaction mixture Vcom-` prising alpha and beta-naphthols and naphthyl ethers, the alpha and beta-naphthols being formed in a Adifferent ratiothan the ratio of the alpha and beta-chloronaphthalenes originallyv present. Y

5. The method of making a mixture of alphaand beta-naphthols which comprises reacting a mono-halo-naphthalene. withr an aqueous hydrolytic base by heating under pressureat'a temperature between 300 and 400 C. in the absence of a catalyst, the reactor surfaces in contact with they reaction mixture beingk composed substantially of metallic iron,'whereby a portion of such Vmono-halo-naphthalene is converted to thecorresponding naphthol and another portion thereof is converted to the isomeric modication thereof, and separating such isomeric'naphthols from the product. v i

6. The methodof making a mixture of alphaand beta-naphthols which comprises reacting a mono-halo-naphthalene with ran aqueous hydrolytic' base by heating under pressure at av temperature between 300 land 400 C. in the absence of catalytically active metallic copper `or copper compounds, vwhereby aportion of such monohalo `compound is converted to the'corr'esponding Ynaphthol and another vportion thereofis converted to the isomeric modification thereof,v andv separating such isomeric naphthcls from the product. l Y Y 7. The method of making a mixture of alphaand beta-naphthols 4which comprises reactinga mono-chloro-naphthalene by heating under pressure at a temperature between 300 and 400 C.

with an aqueous hydrolytic agent from the class consisting of the alkali-metal hydroxides,` carbonates and bor'ates,f in the absence of lcatalytically activeV metallic copper or copper compounds, whereby a portion of such mono-chloro compound is converted to the corresponding naphthol, l

and another portion thereof is converted to the isomeric, Amodiiication thereof, and separatingV f such isomeric naphthols from the product.

8. The method of making a mixture of alphaand beta-naphthols which comprises reacting sure at a temperature between 300 and 400 C.

fwith an aqueous hydrolytic agent selected from the group consisting of. the alkali-metal `hy- 1 vdroxides, carbonates andborates, in the absence* 'of catalytically activemetalliccopper or copperv compounds, whereby a portion of such alphachloro-naphthalene verted to the isomeric beta-naphthol, and separating suchisomeric naphtholsfrom the product.`

' c 9. The methodof making a mixture of alphal and beta-naphthols ywhich comprises reacting compounds, whereby ak portion of beta-chlorolO alpha-chloro-naphthalene by heating under presy is converted to alphanaphthol and another portion thereof is consoif f naphthalene is converted to beta-naphthol 'and i anotherV portion thereof is converted to the ,Y

isomeric alpha-naphthol, and `se'parating'wsuch isomeric naphthols from the-product.

' EDGAR C. BRITTON.

HORACE A. STEARNS. Y 

